EP0930939B1 - ZnS PHOTOCATALYST, ITS PREPARATION AND METHOD FOR PRODUCING HYDROGEN BY USE OF THE SAME - Google Patents

ZnS PHOTOCATALYST, ITS PREPARATION AND METHOD FOR PRODUCING HYDROGEN BY USE OF THE SAME Download PDF

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Publication number
EP0930939B1
EP0930939B1 EP97943211A EP97943211A EP0930939B1 EP 0930939 B1 EP0930939 B1 EP 0930939B1 EP 97943211 A EP97943211 A EP 97943211A EP 97943211 A EP97943211 A EP 97943211A EP 0930939 B1 EP0930939 B1 EP 0930939B1
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Prior art keywords
photocatalyst
hydrogen
accordance
sintering
water
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Expired - Lifetime
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EP97943211A
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German (de)
French (fr)
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EP0930939A1 (en
Inventor
Dae Chul Park
Sang Yoon Lim
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Korea Research Institute of Chemical Technology KRICT
Chunggu Co Ltd
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Korea Research Institute of Chemical Technology KRICT
Chunggu Co Ltd
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    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group metals
    • B01J35/30—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Technical Field
The present invention relates, in general, to a novel photocatalyst and, more particularly, to a photoreaction in which hydrogen can be efficiently and economically produced from water in the presence of a photocatalyst. Also, the present invention is concerned with a method for preparing the photocatalyst and a method for producing hydrogen.
Background Art
Hydrogen is a very important material in the chemical industry. For example, it is used to produce ammonia and to synthesize hydrogen chloride. Also, it is an essential material for the hydrogenation in which unsaturated compounds are converted into saturated ones. In addition, hydrogen plays a pivotal role in improving the quality of petroleum products, that is, in the hydrotreating processes including hydrogen addition, desulfurization, denitrogenation and demetallization. Another example of the use of hydrogen is the contact hydrogenation of carbon dioxide in which carbon dioxide, which causes global warming, is reclaimed, immobilized and reused. In addition, hydrogen is viewed as a pollution-free, clear energy source substituting for existing fossil fuels.
Conventional techniques for obtaining hydrogen include extraction from fossil fuels, such as naphtha, modification of natural gas, reaction of vapor with iron, reaction of water with metal, electrolysis of water and etc. These techniques are economically unfavorable because immense heat or electric energy is required. The conventional techniques have another disadvantage of generating a large quantity of by-products, carbon dioxide or oxygen (upon electrolysis). As mentioned above, carbon dioxide is a serious air pollutant causing the greenhouse effect of the globe. When oxygen is generated, the hydrogen is difficult to separate from the oxygen, owing to which the process becomes complicated. Anyway, such by-products could make it difficult to obtain high purity hydrogen in high yields. Since the hydrogen production using such conventional techniques is usually carried out at relatively high temperatures, most of the related equipments, e.g. reactors and purifying apparatuses, are designed to be resistant to heat and thus, they are very expensive, which is an economically unfavorable factor.
Hydrogen gas can readily escape from the gravity of the earth because it is of low specific gravity and most of it exists in water or inorganic forms. For these reasons, only a small quantity of hydrogen exists in the atmosphere. Therefore, the development of the techniques whereby high purity hydrogen can be efficiently obtained from water is very important in that the urgent problem of exploiting substitute energy sources can be solved and the material for chemical industry can be secured.
Recently hydrogen producing techniques have been developed in which a photocatalyst is used to decompose water into hydrogen and oxygen. However, the prior arts relating to the photocatalyst for producing hydrogen are few published, representatives of which are exemplified by Japanese Pat. Laid-Open Publication Nos. Sho. 62-191045 and Sho. 63-107815.
Japanese Pat. Laid-Open Publication No. Sho. 62-191045 discloses that hydrogen is generated from an aqueous Na2S solution in the presence of a rare-earth element compound by a photolysis reaction. The rare-earth element compound has an advantage of exhibiting an optical catalytic activity in the range of the visible light.
Japanese Pat. Laid-Open Publication No. Sho. describes a photolysis reaction in which a composite oxide of niobium and alkali earth metal is used as a photocatalyst, to generate hydrogen from a methanol solution in water. Likely, this photocatalyst has an advantage of being active in the range of the visible light.
However, these above prior arts are disadvantageous in that the amount of the hydrogen generated is very small.
Korean Pat. Appl'n. No. 95-7721, under the present inventor, which is believed to solve the above problems to some degree, suggests a photocatalyst represented by the following general formula I: Cs(a)/K4Nb6O17 In the presence of the photocatalyst, ultraviolet light is irradiated onto an aqueous solution mixed with oxygen-containing organic compounds, such as formaldehyde and alcohol, acting as a hydrogen-generating promoter, to produce hydrogen.
This technique little affects the environment and can generate hydrogen at low temperatures, e.g. room temperature. However, the oxygen-containing organic compound as a hydrogen-generating promotor, makes it impossible to reuse the reactants.
Disclosure of the Invention
Therefore, it is an object of the present invention to overcome the above problems encountered in prior arts and to provide a novel photocatalyst for producing hydrogen, which is active in the range of the visible light and with which a large quantity of hydrogen is efficiently produced at low temperatures, e.g. room temperature, without using any oxygen-containing organic compound.
It is another object of the present invention to provide a method for preparing the photocatalyst.
It is a further object of the present invention to provide a method for economically producing hydrogen using the photocatalyst.
In accordance with an aspect of the present invention, there is provided a photocatalyst represented by the following general formula II: Pt(a)/Zn[M(b)]S wherein character "a" represents a percentage by weight of Pt in the photocatalyst, ranging from 0.1 to 3.5; character "M" is an element selected from the group consisting of Co, Fe, Ni and P; character "b" represents a mole % of M/Zn, ranging from 0.05 to 30.
In accordance with another aspect of the present invention, there is provided a method for preparing a photocatalyst, as set out in claim 3.
In accordance with a further aspect of the present invention, there is provided a method for producing hydrogen, in which ultraviolet or visible light is irradiated onto a suspension of the photocatalyst in water which contains Na2S as an electron donor and NaH2PO2 as a reducing agent, as set out in claim 7.
Best Mode for Carrying Out the Invention
Acting as a promotor, the M ingredient in the photocatalyst of the present invention is an element selected from the group consisting of Co, Fe, Ni and P, and used at such an amount that the mole % of M/Zn ranges approximately 0.05 to 30. For example, if too little M ingredient is used, the Zn2+ ion in the photocatalyst is reduced to dark gray Zn, losing the catalytic activity. On the other hand, if too much M ingredient is used, the photocatalyst is seriously reduced in the capability of generating hydrogen.
In the photocatalyst of the present invention, Pt serves as an electron acceptor and is used at an amount of 0.1-3.5 % by weight. For example, when the amount of Pt is less than the lower limit, the photocatalyst becomes poor in the production rate of hydrogen as well as lives a short life. On the other hand, if the amount of Pt is over the upper limit, the generation amount of hydrogen cannot increase further and it is economically unfavorable owing to the increased production cost of the catalyst.
As to the amount of zinc and sulfur, it is preferred that the molar ratio of zinc to sulfur ranges from 1:0.1 to 1:2.8 and more preferably from 1:0.6 to 1:1.4. For example, if the molar ratio departs from the ranges, the efficacy of the photocatalyst profoundly becomes poor.
Examples of the Zn-containing compounds include ZnSo4·7H2O and Zn(NO3)2·6H2O while the M-containing compound can be obtained from, for example, Co(NO3)2·6H2O, NiCl2·6H2O, Fe(NO3)2·9H2O, H3PO2 and H3PO4. In the preparation method of the photocatalyst of the invention, the drying and the sintering steps after the control of pH to 7 have an aim of removing the above acidic metal salt solution remaining in the precipitate or other residual acidic solutions.
The etching with acid after the primary sintering is taken in order to remove the oxides which may be formed on the surface of Zn[M]S. Examples of available acid include nitric acid, hydrochloric acid and sulfuric acid with the most preference to nitric acid when considering the convenience of treatment.
Preferably, Zn[M]S is impregnated with Pt by dissolving hydrogen hexachloroplatinate (H2PtCl6) in water, adding Zn[M]S in the water and illuminating ultra violet light on the water. The Pt-impregnated Zn[M]S thus obtained is washed with water until its pH reaches 7, dried at 100-120 °C and sintered to yield the photocatalyst of the invention. Upon sintering, the temperature is preferably in a range of 250-350 °C. For example, if the sintering step is carried out at a temperature lower than the range, the resulting photocatalyst has a short life span. On the other hand, if a too much higher temperature is taken, the resulting photocatalyst is poor in the production rate of hydrogen.
In order to produce hydrogen, for example, 0.15-0.40 moles of Na2 as an electron donor and 0.2-0.5 moles of NaH2PO2 are first dissolved in water and added with the photocatalyst of the present invention. Then, this suspension is irradiated by visible or uv light with stirring. When Na2S and NaH2PO2 are used at an amount smaller than 0.15 moles and 0.40 moles, respectively, the production rate of hydrogen is reduced. On the other hand, when the amounts of Na2S and NaH2PO2 exceed their individual upper limits, the production rate of hydrogen cannot be increased further.
The production of hydrogen using the photocatalyst of the present invention is preferably obtained at a temperature of 10-60 °C in vacuo or under up to 2 atm.
A better understanding of the present invention may be obtained through the following examples which are set forth to illustrate, but are not to be construed as the limit of the present invention.
PREPARATION EXAMPLE I
In 500 ml, 143.77 g of ZnSO4·7H2O and 0.29 g of Co(NO3)2·6H2O were added to give a 0.2 mole % Co/Zn suspension. The suspension was added with H2S as a reactant and stirred to obtain precipitates which were, then, washed with water until its pH reached 7, dried at 110 °C for 12 hours, sintered at 300 °C for 2 hours and etched with nitric acid for 1 hour. The resulting etched, sintered body was again washed with water until the pH reached 7, followed by drying in vacuo at 60 °C, to produce ZnCoS powder.
To the powder, hydrogen hexachloroplatinate (H2PtCl6) was added and irradiated with uv light for 30 min to impregnate the carrier with 2 % by weight of Pt. The Pt/ZnCoS powder thus obtained was again washed with water until the pH reached 7, dried at 110 °C for 12 hours, oxidation-sintered at 300 °C for 2 hours and then, reduction-sintered at 300 °C for 2 hours, to yield a final Pt/ZnCoS photocatalyst.
PREPARATION EXAMPLES II AND III
The procedure of Preparation Example I was repeated using such controlled amounts of Co(NO3)2·6H2O that Co/Zn was 0.6 and 1.0 in mole %, respectively.
PREPARATION EXAMPLES IV TO VI
The procedure of Preparation Example I was repeated except that Fe(NO3)2·9H2O, NiCl2·6H2O and H3PO2, instead of Co(NO3)2·6H2O, were used at such an amount that Fe/Zn, Ni/Zn and P/Zn were 5.0 in mole %, respectively.
EXAMPLES I TO VI
0.5 g of the photocatalysts obtained in Preparation Examples I to VI were suspended in 500 ml of water which contained 0.24 M of Na2S and 0.35 M of NaH2PO2 and stirred at a speed of 400 rpm in a photoreactor of a closed air circulation system. Using a high pressure mercury lamp to illuminate visible light upon the suspension, hydrogen was produced at room temperature under one atmosphere. The amounts of the produced hydrogen were analyzed by gas chromatography and the results are given as shown in Table 1 below.
COMPARATIVE EXAMPLE I
Hydrogen was produced in a similar manner to that of Example I except that the photocatalyst used was prepared in such a way that Co/Zn was contained at an amount of 0.04 mole %. The result is given as shown in Table 1 below.
COMPARATIVE EXAMPLES II TO V
Hydrogen was produced in a similar manner to that of Example I except that the photocatalyst used was prepared in such a way that Co/Zn, Fe/Zn, Ni/Zn and P/Zn were contained at an amount of 40 mole %, each. The results are given as shown in Table 1 below.
EXAMPLE VII
The procedure was repeated using uv light and the result is given as shown in Table 1 below.
EXAMPLE VIII
The procedure was repeated using Na2S at a concentration of 0.15 M and the result is given as shown in Table 1 below.2
COMPARATIVE EXAMPLE VI
The procedure was repeated using Na2S at a concentration of 0.1 M and the result is given as shown in Table 1 below.
EXAMPLE IX
The procedure was repeated using Na2S at a concentration of 0.4 M and the result is given as shown in Table 1 below.
COMPARATIVE EXAMPLE VII
The procedure was repeated using Na2S at a concentration of 0.5 M and the result is given as shown in Table 1 below.
EXAMPLE X
The procedure was repeated using NaH2PO2 at a concentration of 0.2 M and the result is given as shown in Table 1 below.
COMPARATIVE EXAMPLE VIII
The procedure was repeated using NaH2PO2 at a concentration of 0.15 M and the result is given as shown in Table 1 below.
EXAMPLE XI
The procedure was repeated using NaH2PO2 at a concentration of 0.15 M and the result is given as shown in Table 1 below.
COMPARATIVE EXAMPLE IX
The procedure was repeated using NaH2PO2 at a concentration of 0.55 M and the result is given as shown in Table 1 below.
Exam. No. Catalyst Light Amount of Gas (ml/0.5g hr)
I Pt(2wt.%)/Zn[Co(0.2)]S visible 600
II Pt(2wt.%)/Zn[Co(0.6)]S visible 474
III Pt(2wt.%)/Zn[Co(1.0)]S visible 320
IV Pt(2wt.%)/Zn[Fe(5.0)]S visible 848
V Pt(2wt.%)/Zn[Ni(5.0)]S visible 919
VI Pt(2wt.%)/Zn[P(5.0)]S visible 421
C.I Pt(2wt.%)/Zn[Co(0.04)]S visible 78
C.II Pt(2wt.%)/Zn[Co(40)]S visible 280
C.III Pt(2wt.%)/Zn[Fe(40)]S visible 220
C.IV Pt(2wt.%)/Zn[Ni(40)]S visible 206
C.V Pt(2wt.%)/Zn[P(40)]S visible 891
VII Pt(2wt.%)/Zn[Co(0.2)]S UV 520
VIII Pt(2wt.%)/Zn[Co(0.2)]S visible 423
C.VI Pt(2wt.%)/Zn[Co(0.2)]S visible 620
IX Pt(2wt.%)/Zn[Co(0.2)]S visible 625
C.VII Pt(2wt.%)/Zn[Co(0.2)]S visible 510
X Pt(2wt.%)/Zn[Co(0.2)]S visible 433
C.VIII Pt(2wt.%)/Zn[Co(0.2)]S visible 629
XI Pt(2wt.%)/Zn(Co(0.2)]S visible 633
C.IX Pt(2wt.%)/Zn[Co(0.2)]S visible 600
Industrial Applicability
As apparent from the data, the photocatalysts in accordance with the present invention are superior in production rate and life span as well as show activity in the range of the visible light.
The present invention has been described in an illustrative manner, and it is to be understood the terminology used is intended to be in the nature of description rather than of limitation.
Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Claims (8)

  1. A ZnS photocatalyst for the production of hydrogen, represented by the following general formula II: Pt(a)/Zn[M(b)]S wherein character "a" represents a percentage by weight of Pt in the photocatalyst, ranging from 0.1 to 3.5; character "M" is an element selected from the group consisting of Co, Fe, Ni and P; character "b" represents a mole % of M/Zn, ranging from 0.05 to 30.
  2. A ZnS photocatalyst in accordance with claim 1, wherein said b ranges from 0.1 to 2.8.
  3. A method for preparing a photocatalyst in accordance with claim 1, comprising the steps of: dissolving Zn-containing and M-containing compounds (wherein M is selected from Co, Ni, Fe and P) in water in such a way that M/Zn ranges, in mole %, from 0.05 to 30; adding H2S or Na2S as a reactant in the solution with stirring to precipitate Zn[M]S; washing the precipitate with water until its pH reaches 7 and drying the precipitate; sintering it at 250-350 °C for 1-3 hours; etching it with acid; washing it with water until the pH reaches 7 and drying it; adding a liquid Pt-containing compound to the Zn[M]S and impregnating Pt in the Zn[M]S at an amount of about 0.1-3.5 % by weight by illumination with uv light; washing the Pt-impregnated Zn[M]S until its pH reaches 7 and subjecting it to drying and sintering.
  4. A method in accordance with claim 3, wherein said M-containing compound comprises Co(NO3)2·6H2O, NiCl2·6H2O, Fe(NO3)2·9H2O, H3PO2 and H3PO4.
  5. A method in accordance with claim 3, wherein said sintering step comprises a sequence of oxidation sintering and reduction sintering.
  6. A method in accordance with claim 3, wherein said Zn-containing compound comprises ZnSO4·7H2O and Zn(NO3)2·6H2O.
  7. A method for producing hydrogen, in which ultraviolet or visible light is irradiated onto a suspension of the photocatalyst in accordance with claim 1 in water, which contains 0.15-0.40 M of Na2S as an electron donor and 0.2-0.5 M of NaH2PO2 as a reducing agent.
  8. A method in accordance with claim 7, wherein hydrogen is produced at a temperature of 10-60 °C in vacuo or under up to 2 atm.
EP97943211A 1996-10-07 1997-10-06 ZnS PHOTOCATALYST, ITS PREPARATION AND METHOD FOR PRODUCING HYDROGEN BY USE OF THE SAME Expired - Lifetime EP0930939B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR4421496 1996-10-07
KR1019960044214A KR100202238B1 (en) 1996-10-07 1996-10-07 Novel zns photocatalyst, method thereof and production of hydrogen gas
PCT/KR1997/000187 WO1998015352A1 (en) 1996-10-07 1997-10-06 NOVEL ZnS PHOTOCATALYST, PREPARATION THEREFOR AND METHOD FOR PRODUCING HYDROGEN BY USE OF THE SAME

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EP0930939A1 EP0930939A1 (en) 1999-07-28
EP0930939B1 true EP0930939B1 (en) 2003-01-08

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US (1) US6077497A (en)
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JP (1) JP3395149B2 (en)
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BR (1) BR9711874A (en)
CA (1) CA2267195C (en)
DE (1) DE69718332T2 (en)
ES (1) ES2191201T3 (en)
RU (1) RU2152822C1 (en)
WO (1) WO1998015352A1 (en)

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KR100288647B1 (en) * 1998-09-09 2001-09-17 김시학 Zinc sulfide-producing photocatalyst for producing hydrogen and its production method, and hydrogen production method using the same
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US20080146965A1 (en) 2003-08-11 2008-06-19 Salvatore Privitera Surgical Device for The Collection of Soft Tissue
DE10000716A1 (en) * 2000-01-11 2001-07-12 Stefan Haegel Hydrogen and oxygen production from water using solar energy is effected in membrane-separated compartments with only one compartment containing a photosensitizer
KR100342856B1 (en) * 2000-02-22 2002-07-02 김충섭 CdZnMS photocatalyst added with cation for water decomposition and preparation there for and method for producing hydrogen by use of the same
US6297190B1 (en) * 2000-02-23 2001-10-02 Korea Research Institute Of Chemical Technology ZnS photocatalyst, preparation therefor and method for producing hydrogen by use of the same
JP4191373B2 (en) * 2000-09-01 2008-12-03 独立行政法人科学技術振興機構 Method for producing highly active photocatalyst and method for treating hydrogen sulfide for recovering hydrogen gas with low energy using highly active photocatalyst
JP5106721B2 (en) * 2001-04-11 2012-12-26 独立行政法人科学技術振興機構 Method for producing photocatalyst and method for treating hydrogen sulfide using the photocatalyst
US20070196268A1 (en) * 2006-02-22 2007-08-23 Smith John R Thermal activation of photocatalytic generation of hydrogen
KR100744636B1 (en) * 2006-08-16 2007-08-01 (재)대구경북과학기술연구원 Method for preparing of zns-zno photocatalyst activated in the visible light
CN102000591B (en) * 2010-11-03 2012-07-25 哈尔滨工业大学 Composite photocatalyst and preparation method thereof
CN102259030B (en) * 2011-05-31 2013-05-22 哈尔滨工业大学 Composite photocatalyst for hydrogen production by hydrolysis in visible light and method for preparing composite photocatalyst
CN102389824B (en) * 2011-10-09 2013-06-12 哈尔滨工业大学 Indium-based sulfide composite photocatalyst and preparation method thereof
US9593053B1 (en) 2011-11-14 2017-03-14 Hypersolar, Inc. Photoelectrosynthetically active heterostructures
JP2013154333A (en) * 2012-01-31 2013-08-15 Toyota Motor Corp Method and apparatus for producing hydrogen and oxygen by decomposing water with photocatalyst
US10100415B2 (en) 2014-03-21 2018-10-16 Hypersolar, Inc. Multi-junction artificial photosynthetic cell with enhanced photovoltages
CN104353470B (en) * 2014-11-14 2017-03-22 武汉钢铁(集团)公司 Nano ZnNiInS solid solution photocatalyst and preparation method thereof
CN105944737A (en) * 2016-05-18 2016-09-21 哈尔滨工业大学 Ni-doped ZnS photic light-driven hydrogen production catalyst preparation method
CN109641744A (en) * 2016-09-01 2019-04-16 日立化成株式会社 The manufacturing method of hydrogen and the manufacturing method of steel

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KR19980025911A (en) 1998-07-15
CN1235562A (en) 1999-11-17
JP2000503595A (en) 2000-03-28
DE69718332D1 (en) 2003-02-13
DE69718332T2 (en) 2003-10-16
WO1998015352A1 (en) 1998-04-16
RU2152822C1 (en) 2000-07-20
CN1108866C (en) 2003-05-21
BR9711874A (en) 1999-08-24
US6077497A (en) 2000-06-20
CA2267195A1 (en) 1998-04-16
JP3395149B2 (en) 2003-04-07
ES2191201T3 (en) 2003-09-01
CA2267195C (en) 2002-11-12
EP0930939A1 (en) 1999-07-28
KR100202238B1 (en) 1999-06-15

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